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1.
Fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomer [RF-(DOBAA)n-RF] reacted with hibitane in methanol at 90 °C to afford RF-(DOBAA)n-RF oligomeric nanoparticles-encapsulated hibitane in good isolated yields. These fluorinated oligomeric particles-encapsulated hibitane were nanometer size-controlled very fine particles, and were found to exhibit a good dispersibility and stability in a wide variety of traditional organic solvents including fluorinated aliphatic solvents. Each dispersed solution with fluorinated nanoparticles afforded transparent colorless solution. These fluorinated nanoparticles were also found to exhibit a good antibacterial activity, and were applied to the surface modification of traditional organic polymers such as poly(methyl methacrylate).  相似文献   

2.
Fluoroalkyl end-capped vinyltrimethoxysilane oligomeric nanocomposites having biphenylene units [R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2)] were prepared by the sol-gel reaction of the corresponding oligomer [R(F)-(VM)(n)-R(F)] with 4,4'-bis(triethoxysilyl)-1,1'-biphenyl [Ar-Si(OEt)(3)] under alkaline conditions. R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were applied to the surface modification of PMMA to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission ability on the surface. Methanol sol solutions of R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites were effective for the surface modification of glass through the dipping technique to exhibit good oleophobicity with superhydrophobicity on the modified glass surface. On the other hand, 1,2-dichloroethane sol solutions enabled R(F)-(VM-SiO(2))(n)-R(F)/Ar-SiO(2) nanocomposites to exhibit both superhydrophobic and superoleophobic characteristics on the modified surface through dipping the glass in these sol solutions.  相似文献   

3.
4.
Thiophene monomer reacted with ferric chloride in the presence of a variety of fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers [RF-(DOBAA)x-RF] to afford nanometer size-controlled RF-(DOBAA)x-RF oligomers-polythiophene composites [RF-(DOBAA)x-RF/PTh]. RF-(DOBAA)x-RF/PTh nanocomposites thus obtained were demonstrated to have a good dispersibility and stability in methanol to give a transparent brown solution. In addition, these fluorinated nanocomposites were applied to the surface modification of common organic polymers such as poly(methyl methacrylate), and were dispersed regularly above the polymer surface.  相似文献   

5.
Calcium chloride reacted with sodium carbonate in the presence of a variety of self-assembled molecular aggregates formed by fluoroalkyl end-capped acrylic acid, 2-methacryloyloxyethane sulfonic acid, dimethylacrylamide, and acryloylmorpholine oligomers in aqueous solutions to afford the corresponding fluorinated oligomers/calcium carbonate composites in excellent to moderate isolated yields. These fluorinated calcium carbonate composites thus obtained were shown to have a good dispersibility not only in water but also in traditional organic media including fluorinated solvents. Dynamic light scattering measurements (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that these fluorinated composites are nanometer-size-controlled particles and well dispersed in these media. Cross-linked fluoroalkyl end-capped acrylic acid co-oligomer containing poly(oxyethylene) units was also applied to the preparation of new cross-linked fluorinated calcium carbonate nanocomposites under similar conditions. The obtained cross-linked fluorinated calcium carbonate nanocomposites were found to have an extremely higher dispersibility in aqueous and organic media including fluorinated solvents, compared to that of the corresponding fluoroalkyl end-capped oligomer nanocomposites. In particular, it was verified that these fluorinated calcium carbonate nanocomposites are applicable to the dispersion above poly(methyl methacrylate) (PMMA) film surface. Interestingly, field-emission SEM (FE-SEM) images of the cross-section of the modified PMMA films showed that calcium carbonate particles dispersed into these PMMA films could be arranged regularly above the modified film surface. More interestingly, cross-linked fluorinated oligomeric aggregates were able to provide suitable host moieties for the crystallization of calcium carbonate.  相似文献   

6.
A variety of fluoroalkyl end-capped oligomers were applied to the preparation of fluorinated oligomer/hydroxyapatite (HAp) composites (particle size: 38-356 nm), which exhibit a good dispersibility in water and traditional organic solvents. These fluoroalkyl end-capped oligomer/HAp composites were easily prepared by the reactions of disodium hydrogen phosphate and calcium chloride in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers in aqueous solutions. In these fluorinated HAp composites thus obtained, fluoroalkyl end-capped acrylic acid oligomers and 2-methacryloyloxyethanesulfonic acid oligomer/HAp nanocomposites afforded transparent colorless solutions toward water; however, fluoroalkyl end-capped N,N-dimethylacrylamide oligomer and acryloylmorpholine oligomer were found to afford transparent colorless solutions with trace amounts of white-colored HAp precipitants under similar conditions. HAp could be encapsulated more effectively into fluorinated 2-methacryloyloxyethanesulfonic acid oligomeric aggregate cores to afford colloidal stable fluorinated oligomer/HAp composites, compared to that of fluorinated acrylic acid oligomers. These fluorinated oligomer/HAp composites were applied to the surface modification of glass and PVA to exhibit a good oleophobicity imparted by fluorine. HAp formation was newly observed on the modified polyethylene terephthalate film surface treated with fluorinated 2-methacryloyloxyethanesulfonic acid oligomers and acrylic acid oligomer/HAp composites by soaking these films into the simulated body fluid.  相似文献   

7.
Fluoroalkyl end-capped vinyltrimethoxysilane oligomer/anatase titanium oxide nanocomposite-encapsulated low molecular weight aromatic compounds [RF-(VM-SiO2)n-RF/an-TiO2/Ar-H] were prepared by the sol–gel reactions of the corresponding oligomer in the presence of anatase titanium oxide nanoparticles (an-TiO2) and the aromatic compounds such as bisphenol A [BPA], 1,1′-bi(2-naphthol) [BINOL], and fullerene under alkaline conditions. Thermogravimetric analyses measurements show that RF-(VM-SiO2)n-RF/an-TiO2 nanocomposite-encapsulated BPA and BINOL, in which the theoretical contents in the composites are 25?~?32 %, were found to give no weight loss corresponding to the contents of these aromatic compounds even after calcination at 800 °C. On the other hand, the corresponding nanocomposite-encapsulated fullerene exhibited weight loss behavior related to the presence of fullerene under similar conditions; however, UV–vis spectra showed the presence of the residual fullerene in the composites even after calcination. An-TiO2 in these fluorinated nanocomposites can keep its crystalline structure without phase transformation into rutile even after calcination at 1,000 °C, although the parent an-TiO2 nanoparticles underwent a complete phase transformation into rutile under similar conditions. Notably, RF-(VM-SiO2)n-RF/an-TiO2/Ar-H nanocomposites can give a good photocatalytic activity even after calcination at 1,000 °C for the decolorization of methylene blue under UV light irradiation. More interestingly, these fluorinated nanocomposites before and after calcination were found to exhibit a higher photocatalytic activity at the initial UV light irradiation from 1 to 3 min than that of the corresponding RF-(VM-SiO2)n-RF/an-TiO2 nanocomposites under similar conditions.
Figure
Encapsulated BPA and BINOL in the nanocomposites exhibit no weight loss even after calcination at 800 °C, and RF-(VM-SiO2)n-RF/an-TiO2/Ar-H nanocomposites before and after calcination at 1,000 °C can give a higher photocatalytic activity than that of RF-(VM-SiO2)n-RF/an-TiO2 nanocomposites. Notably, the photocatalytic activity of RF-(VM-SiO2)n-RF/an-TiO2/C60 nanocomposites after calcination increased by about 2.5-fold, compared with that of RF-(VM-SiO2)n-RF/an-TiO2 nanocomposites.  相似文献   

8.
Journal of Sol-Gel Science and Technology - Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [R F-(CH2CHSi(OMe)3) n -R F; R F?=?CF(CF3)OC3F7, n?=?2, 3: R F-(VM) n -R F...  相似文献   

9.
Novel fluoroalkyl end‐capped vinyltrimethoxysilane oligomer/hydroxyapatite (HAp) nanocomposites were prepared by the reaction of calcium nitrate tetrahydrate and phosphoric acid in the presence of the corresponding oligomer. These fluorinated oligomer/HAp composites thus obtained are nanometer size‐controlled fine particles (83–173 nm), and were found to exhibit good dispersibility in methanol, ethanol, and isopropyl alcohol. These fluorinated HAp nanocomposites were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleophobic characteristics imparted by fluorine on their surface. In addition, the surface structural changes of the modified polyethylene terephtalate and PMMA films treated with these fluorinated nanocomposites before and after soaking in a simulated body fluid (SBF) were analyzed by using SEM, XRD, and EDX to observe the formation of spherical HAp deposits on the surface. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

10.
New fluoroalkyl end-capped 2-acrylamido-2-methylpropanesulfonic acid oligomers/clay composites were prepared by reaction of fluoroalkanoyl peroxide with the corresponding monomer in the presence of clay in aqueous solutions. These obtained fluorinated composites were nanometer size-controlled and were found to exhibit a good dispersibility in water and polar organic solvents such as methanol. The contents of clay in these nanocomposites were estimated to be 3~19% by the thermogravimetric analysis measurements. X-ray diffraction spectra showed the successful intercalation of fluorinated oligomers into the interlayer spaces of clay. These fluorinated clay nanocomposites were applied to the surface modification of poly(vinyl alcohol). In addition, these fluorinated nanocomposites were found to interact with methylene blue effectively to afford the fluorinated oligomers/clay/methylene blue nanocomposites.  相似文献   

11.
We have studied on the solubilization of single-walled carbon nanotubes (SW-CNTs) into aqueous and organic media by the use of a variety of nanometer size-controlled fluorinated self-assemblies, which were formed by the aggregations of end-capped fluoroalkyl segments in fluoroalkyl end-capped acrylic acid oligomers [RF-(ACA)n-RF], N,N-dimethylacrylamide oligomers [RF-(DMAA)n-RF], acryloylmorpholine oligomers [RF-(ACMO)n-RF], and N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers [RF-(DOBAA)n-RF]. Fluorinated self assemblies formed in organic media (colorless solutions) could solubilize SW-CNTs into organic media to afford the transparent pale yellow solutions. The dynamic light scattering measurements showed that the size of fluorinated self-assemblies increased after the solubilization of SW-CNTs into organic media. It was suggested that the solubilization of SW-CNTs into organic media is due to the encapsulation of SW-CNTs into fluorinated assemblies. Fluorinated assemblies were also able to solubilize SW-CNTs into water to give the transparent gray solutions. Among a variety of fluorinated assemblies, fluorinated assemblies formed by RF-(ACMO)n-RF [RF = CF(CF3)OC6F13] oligomer was more effective for the solubilization of SW-CNTs into both aqueous and organic media. Contact angle measurements of dodecane and the fluorescence spectra for poly(methyl methacrylate) cast film modified by fluorinated self-assemblies—SW-CNTs complexes showed that SW-CNTs are dispersed above the PMMA surface.  相似文献   

12.
Copper(II) oxide reacted with hydrazine in the presence of fluoroalkyl end-capped oxime-blocked isocyanato cooligomer containing adamantyl segments at 90 °C for 30 min in ethylene glycol, and the deprotecting reaction of the cooligomer in the resulting product at 120 °C for 15 min was found to afford the colloidal red-brown colored cross-linked fluorinated cooligomer/Cu nanocomposites, which were stabilized by fluoroalkyl end-capped cooligomer containing benzotriazole segments. On the other hand, the corresponding cross-linked fluorinated cooligomer possessing no adamantyl segments could not afford the copper nanocomposites under similar conditions. Dynamic light scattering measurements and TEM photography of these cross-linked fluorinated cooligomer/Cu composites showed that these composites are nanometer size-controlled very fine nanoparticles. These fluorinated Cu nanocomposites have a good dispersibility and stability in mixed solvents of ethylene glycol and methanol for two weeks under air atmosphere conditions. In addition, these fluorinated Cu nanocomposite powders have been found to be stable for more than three months.  相似文献   

13.
A variety of fluoroalkyl end-capped oligomers, such as fluoroalkyl end-capped acrylic acid oligomer [RF-(ACA) n -RF], acryloylmorpholine oligomer [RF-(ACMO) n -RF], 2-acrylamido-2-methylpropanesulfonic acid oligomer [RF-(AMPS) n -RF], 2-(methacryloyloxy)ethanesulfonic acid oligomer [RF-(MES) n -RF], and N,N-dimethylacrylamide oligomer [RF-(DMAA) n -RF], were applied to the autoreduction of gold ions to give the corresponding oligomers/gold nanocomposites, of whose sharp plasmon absorption bands are observed around 535 nm. In these fluorinated oligomers, RF-(ACA) n -RF oligomer and RF-(ACMO) n -RF were effective for the one-pot preparation of the gold nanoparticles under very mild conditions; although the other fluorinated oligomers and the corresponding non-fluorinated–(ACMO) n -oligomer were unable to afford the gold nanoparticles. RF-(ACA) n -RF/SiO2 nanocomposites and RF-(ACMO) n -RF/SiO2 nanocomposites, which were prepared by the sol–gel reactions of tetraethoxysilane in the presence of silica nanoparticles and the corresponding oligomers under alkaline conditions, were also applied to the encapsulation of gold nanoparticles into these fluorinated nanocomposite cores through the autoreduction of gold ions at room temperature. Interestingly, these fluorinated oligomers/silica nanocomposite-encapsulated gold nanocomposites before and after calcination at 800 °C were found to exhibit the same plasmon absorption band around 525 nm. RF-(MES) n -RF oligomer and RF-(AMPS) n -RF oligomer are not suitable for the autoreduction of gold ions; however, RF-(MES)n-RF[or RF-(AMPS) n -RF]/polyaniline [PAn] nanocomposites, which were prepared by the polymerization of aniline initiated by ammonium persulfate in the presence of the corresponding oligomer, enabled the formation of gold nanoparticles through the oxidation of PAn in the composites at room temperature. The reversible conformational change of PAn in the nanocomposites from the polyemeraldine salt to the oxidized pernigraniline base was observed during such oxidation process. Graphical abstract
?  相似文献   

14.
Fluoroalkyl end-capped vinylphosphonic acid cooligomers-encapsulated magnetite nanocomposites were prepared by the magnetization of aqueous ferric and ferrous ions in the presence of the corresponding fluorinated cooligomers and magnetic nanoparticles under alkaline conditions. These fluorinated cooligomers magnetic composites are nanometer size-controlled very fine particles and have a good dispersibility and stability in water and traditional organic solvents. These fluorinated nanocomposites were also applied to the surface modification of poly(methyl methacrylate) to exhibit a good oleophobicity imparted by fluorine on their surface. Fluoroalkyl end-capped 2-methacryloyloxyethanesulfonic acid oligomer-encapsulated magnetite nanocomposites and fluoroalkyl end-capped 2-acrylamide-2-methylpropanesulfonic acid oligomer-encapsulated magnetite nanocomposites were prepared in good isolated yields by the magnetization of iron chlorides in the presence of the corresponding oligomers and magnetic nanoparticles under similar conditions. Colloidal stability of these fluorinated nanocomposites thus obtained in water was demonstrated to become extremely higher than that of fluorinated vinylphosphonic acid cooligomers/magnetic nanocomposites.  相似文献   

15.
Fluoroalkyl end‐capped vinyltrimethoxysilane oligomer [RF‐(VM)nRF] reacted with boric acid to afford the corresponding fluorinated oligomeric silica/boric acid nanocomposite [RF‐(VM? SiO2)nRF/B(OH)3] fine particles with mean diameter: 36–105 nm. The obtained RF‐(VM? SiO2)nRF/B(OH)3 nanocomposites were applied to the encapsulation of low molecular weight organic compounds such as diphenylsilanediol, 1,1′‐bi‐2‐naphthol, 4,4′‐biphenol, bisphenol A, bisphenol F, bisphenol AF, biphenyl, dibenzyl, and pentaerythritol into these nanocomposite cores to provide the corresponding fluorinated oligomeric silica/boric acid nanocomposites—encapsulated these organic molecules. Interestingly, the obtained nanocomposites were found to exhibit no weight loss behavior corresponding to the contents of these guest molecules even after calcination at 800 °C, although these nanocomposites were isolated through no purification process. The RF‐(VM? SiO2)nRF nanocomposites—encapsulated these organic guest molecules were prepared under similar conditions. However, it was demonstrated that these nanocomposites can provide the clear weight loss corresponding to the contents of these guest molecules in the nanocomposites after calcination at 800 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3835–3845  相似文献   

16.
Nanometer size-controlled gold particles were prepared under mild conditions by reducing the corresponding metal precursor in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped N-(1,1-dimethyl-3-oxobutyl)acrylamide oligomers. The stable gold nanoparticles protected by these fluorinated molecular aggregates were applied to the dispersion above the poly(methyl methacrylate) film surface.  相似文献   

17.
Cross-linked fluoroalkyl end-capped oligomeric nanocomposites possessing aromatic siloxane segments as core units [RF-oligomer/Ar-SiO 2 ] exhibited an encapsulation ability toward organic dyes such as methylene blue (MB), rhodamine B (RB), 4-hydroxyazobenzene-4′-sulfonic acid sodium salt, and methyl orange (MO). In these organic dyes, MB and RB are effectively encapsulated into these nanocomposites in aqueous solutions. RF-oligomer/Ar-SiO 2 nanocomposite-encapsulated organic dyes were found to exhibit a controlled releasing characteristic toward these encapsulated dyes, and encapsulated MB was not released into water; however, this encapsulated dye was smoothly released into acetone under similar conditions. Interestingly, RF-oligomer/Ar-SiO 2 nanocomposites possessing biphenylene segments as core units were able to exhibit not a photostable characteristic but extremely higher photodegradation ability toward MO under UV light irradiation.  相似文献   

18.
Fluoroalkyl end‐capped N,N‐dimethylacrylamide oligomer and N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer were reacted with phenylene‐ and biphenylene‐bridged ethoxysilanes under alkaline conditions to yield cross‐linked fluoroalkyl end‐capped oligomeric composites possessing aromatic siloxane segments as core units. These isolated fluorinated composite powders were found to be nanometer size‐controlled fine particles with a good dispersibility and stability in water and organic solvents. Nitrogen adsorption–desorption isotherms confirmed the presence of micropores in these nanocomposites; the micropore size estimated by the HK method was 0.7–0.8 nm. Interestingly, fluorinated nanocomposites possessing a higher micropore volume ratio were found to exhibit a selective encapsulation ability of fullerene into their composite cores. These fluorinated nanocomposites were also applied to the surface modification of poly(methyl methacrylate) film, resulting in a good oleophobicity imparted by fluorine on the surface. In addition, fluorescence emission was visibly observed only from the modified PMMA film surface treated with fluorinated nanocomposites possessing biphenylene units when irradiated by light. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

19.
A variety of fluoroalkyl end-capped oligomers were prepared under mild conditions by the use of fluoroalkanoyl peroxide as a key intermediate. These oligomers can form the self-assembled molecular aggregates with the aggregations of end-capped fluoroalkyl groups in aqueous and organic media. Fluorinated self-assembled molecular aggregates containing carboxyl and sulfo groups were suggested to interact with positively charged HIV-1 to exhibit a potent anti-HIV-1 activity in vitro. In contrast, fluoroalkyl end-capped oligomers containing cationic segments exhibited not only the unique surface active properties imparted by fluorine as well as the usual low-molecular fluorinated surfactants, but also high surface antibacterial activity. Fluoroalkyl end-capped oligomers containing betaine-type segments were found to cause a gelation where the strong aggregation of the end-capped fluoroalkyl groups is involved in establishing the physical gel network in water and polar organic solvents under non-crosslinked conditions. Similarly, fluoroalkyl end-capped oligomers containing hydroxyl groups could cause a gelation, where the aggregation of fluoroalkyl groups and hydrogen-bonding interaction is involved in establishing a physical gel network in water and polar organic solvents under non-crosslinked conditions. Fluoroalkanoyl peroxide is also a convenient tool for the preparation of new fluoroalkyl end-capped oligomers containing recognition moieties such as diacetone segments. These fluorinated oligomers containing recognition moieties could form the self-assembled molecular aggregates to recognize selectively the hydrophilic amino and N,N-dimethylamino compounds as guest molecules.  相似文献   

20.
Cross-linked fluoroalkyl end-capped cooligomers possessing double decker-type aromatic silsesquioxane segments as core units [RF-(Ar-SiSQ) x -(Co-M) y -RF] were prepared under mild conditions by the cooligomerizations of fluoroalkanoyl peroxide with the corresponding aromatic silsesquioxane possessing bifunctional vinyl groups (Ar-SiSQ) and comonomers (Co-M) such as acryloylmorpholine (ACMO), N,N-dimethylacrylamide (DMAA) and N-(1,1-dimethyl-3-oxobutyl)acrylamide (DOBAA). Interestingly, these cross-linked fluorinated cooligomers thus obtained were found to form the nanometer size-controlled nanoparticles with a good dispersibility in a variety of solvents including fluorinated aliphatic solvents. These fluorinated cooligomeric nanoparticles were demonstrated to have red-shifted fluorescent emissions related to the presence of aromatic silsesquioxane segments, compared with that of parent aromatic silsesquioxane, indicating that each aromatic moiety in these nanoparticles can interact effectively with each other through the π–π stacking between the aromatic moieties to afford the red-shifted fluorescent emissions. These fluorinated nanoparticles were also applied to the surface modification of poly(methyl methacrylate) (PMMA) to exhibit not only a good oleophobicity imparted by fluorine but also a fluorescent emission behavior related to aromatic silsesquioxane segments in nanoparticles on the modified PMMA surface. More interestingly, cross-linked RF-(Ar-SiSQ) x -(DOBAA) y -RF cooligomeric nanoparticles interacted with fluorescein to give the corresponding fluorinated cooligomeric particles/fluorescein nanocomposites in methanol. These fluorinated fluorescein nanocomposites were found to afford an extraordinarily enhanced light absorption (λ max = 441 nm), compared with that of fluoroalkyl end-capped DOBAA oligomer [RF-(DOBAA) n -RF] possessing no aromatic silsesquioxane segments.  相似文献   

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